Permanent deformation of hair



United States Patent 3,157,575 PERMAN E T DEFiBRMATlQN (3F HAR CharlesZvialr, Franconville, Seine-et-Oise, Md Jean Benet, Le Blanc-Mesnil,Seine-et-Qise, France, assignors to Societe anonyme elite: LGrenl,Paris, France No Drawing. Filed July 25, 196i Ser. No. 169,153 Claimspriority, application France .lnly 23, 1959 14- Claims. (Cl. 167-871)This invention relates to processes for the permanent deformation ofkeratinous material and more particularly to the permanent waving ofhuman hair, to aqueous solutions for use in the said processes and toprocesses for the production of the said solutions.

In the permanent deformation of hair, and more particularly in thereduction of the cystine bridges in keratin, it has previously beenknown to use reducing solutions of ammonium thioglycollate containingammonium carbonate. The pH value of such solutions, which may varybetween about 7.7 and 9, depends to a large extent upon their content offree ammonia and carbon dioxide.

These reducing solutions, which can be used around pH 8, have definiteadvantages over the previously employed solutions of ammoniumthioglycollate lacking ammonium carbonate which have pH values betweenabout 9.2 and 9.5. One advantage is the lower risk of damage to the haircaused by hydrolysis of the keratin, because the hydrolysis rate islower at, say, pH 8 than at pH values above 9. Another advantage isthat, in the case of sensitive skins, most of the irritations of thescalp and or" the hands of the operator are substantially avoided usingsolutions of about pH 8. Further, solutions having lower pH valuesgenerally have much less objectionable odour than those, for example,having pH values above 9.2.

Nevertheless, reducing solutions of relatively low pH value do havecertain disadvantages which render their use inconvenient. For example,their ability to impart a permanent curl to constrained hair isrelatively low at about pH 8, so that it is necessary to prolong theduration of application, or to use a heating hood, or to increase theconcentration of the reducing agent in the solution. Regardless of themethod adoptethe waving operation becomes more difficult.

it has now been found that the aforesaid disadvantages may be obviatedby replacing the ammonia, both in its function as a neutralising agentfor the acid reducing agent and in the form of ammonium carbonate, by anorganic base such as guanidine, monoethylamine, monoethanolamine,monoisopropanolamine, diethanolamine or morpholine.

According to a first feature of the present invention, therefore, anaqueous solution for use in efiecting the permanent deformation of hairor other keratinous material comprises a salt of a mercaptocarboxylicacid with an organic base and a carbonate of an organic base, the pHvalue of the solution being from 7 to 9.

According to a further feature of the present invention a method ofimparting a permanent deformation to hair or other keratinous materialcomprises constraining the material to a desired configuration, treatingthe constrained material at room temperature with an aqueous solution asjust set forth and thereafter setting the configuration of the materialby oxidation.

A 3,1575% Patented Nov. 17., 1964 ice As mercaptocarboxylic acids thereare preferably em ployed thioglycollic acid or thiolactic acid and theseare preferably employed in concentrations from 0.3 to 1.5 mols perlitre. The preferred pH value of the solution is from 7.5 to 8.5. Theconcentration of the carbonate of the organic base may advantageouslyvary between 0.1 and 1.5 mols per litre.

Various methods for the preparation of the solutions of the presentinvention may be employed. Thus, for example, it is possible exactly toneutralise a mercaptocarboxylic acid solution by means of an organicbase and then to add the required quantity of the carbonate of anorganic base. it is also possible to add to a solution of the acid aslight excess of the organic base over that required to neutralise theacid. The excess base may then be converted into its carbonate byintroducing into the solution the necessary quantity of carbon dioxidethrough a distributing head. In either procedure the pH value of thesolution can be adjusted to between 7 and 9 by regulating the quantityof carbon dioxide introduced.

The solutions obtained by carrying out the procedures indicated aboveare applied to hair or other keratinous material at room temperature bythe method usually adopted in permanent waving with, for example, ammonium thioglycollate, i.e., in a first phase the locks of hair areimpregnated with the waving solution, they are wound on curlers and eachcurler is then saturated with the solution which is allowed to act for 5to 20 minutes, depending upon the nature of the hair. The hair is thenrinsed and thereafter treated with an oxidising solution in accordancewith the usual technique. There is thus obtained a springy curl whichhas good resistance to humidity and shampoos.

The following examples, which describe the preparation of cold wavingsolutions which may be used in the conventional manner indicated above,will serve to illustrate the invention:

Example I A solution is prepared having the following composition:

G. Thioglycollic acid 8 Monoethanolamine 10 Water to mfie cc.

A current of CO is slowly introduced into this solution through adistributing head until the solution has a pH of 8.2. 7

Example 11 The following solution is prepared:

G. Thioglycollic acid 8 ls lorpholine 16 The following solution isprepared:

G. Thioglycollic acid 8 Monoethanolamine 7.8

Water to make 100 cc.

CO is introduced until the solution has a pH value of 7.6.

'Thioglycollic acid 3 Example IV The following solution is prepared:

Diethanolamine Water to make 100 cc.

CO is introduced until the solution has a pH value of 8.2.

7 Example V The following solution is prepared:

Thioglycollic acid 8 Guanidine carbonate 8.5

Water to make 100 cc.

CO is introduced until the solution has a pH value of 7.3.

Example VII 1 The following solution is prepared:

. G. Thioglycollic acid 8 Ethylamine 5.6 Morpholine 6 Water to make 100cc. CO is introduced until the solution has a pH value of 8.2.

I Example VII! The following solution is prepared:

6. Thioglycollic acid 8 Monoethanolamine 6.8

Morpholine a 6 Water to make 100 cc.

CO is introduced until the solution has a pH value of 8.2.

7 Example IX The following solution is prepared:

. G Thioglycollic acid a 8 Ethylamine 5.6 Diethanolamine 7.35

Water to make 100 cc.

is introduced until the solution has a pH value of 8.2. What We claimis:

,1. An aqueous solution for use'in efiecting the perina: 'nentdeformation of hair and other keratinous material comprising a salt of amercaptocarboxylic acid selected from the group consisting ofthioglycollic acid and thiolacetic acid with at least one organicbaseselected from the group consisting of guanidine, monoethylarnine,monoethanolaminc, fdiethanolamine, monoisopropanolamine and morpholineand a carbonate of said organic base, the pH value of the solution beingfrom 7 to-9L 2. An aqueous solution for use in efiecting the permanentdeformation. of hair and other keratinous material comprisin'g'a salthaving a concentration of 0.3. to 1.5 g mols per litre of amercaptocarboxylic acid selected from .the group consisting ofthioglycollic acid and thiolacetic acid With at least one organic baseselected from the group consisting of guanidine, monoethylamine,monoethanolamine, diethanolarnine, monoisopropanolamine and morpholin'e,and acarbonate of said organic base, the pH value of the solution beingfrom 7 to 9.

3. An aqueous solution for usein'eiiecting the permanent deformation ofhair and other keratinous materi 1 4. V comprising a salt of,mercaptocarboxylic acid selected from the group consistingofthioglycollic acid and thiolacetic acid with at least one organic baseselected from the group consisting of uanidine, monoethylamine'monoamineand morpholine, and a carbonate of said organic base, the pH value ofthe solution being from 7.5 to 8. 5. 5. An aqueous solution foreffecting the permanent deformation of hair and otherkeratinous materialcomprising a salt having a concentration of 0.3 to 1.5 mols per litre ofa mercaptocarboxylic acid selected from the group consisting ofthioglycollic acid and thiolacetic acid with at least one organic baseselected from the group consisting of guanidine, monoethylamine,monoethanolamine, diethanolamine, monoisopropan'olamine and rnOrpholineand a carbonate of saidorganic base having a concentration of 0.1 to 1.5mols per litre, the pH value of the solution being from 7.5 to 8.5.

6. A process for the preparation of an aqueous solu: tion for effectingthe permanent deformation of hair and other keratinous materialcomprising passing carbon dioxideinto an aqueous solution containing amercaptocarboxylic acid selected from the group consisting ofthioglycollic acid and ,thiolacetic acid and at least one organic baseselected from the group consisting of guanidine, monoethylarnine,monoethanolamine, diethanolamine, monoisopropanolamine and morpholine,until the solution attains a pH value from 7 to 9. V

7. A process for the preparation of an aqueous solution for etiectingthe permanent deformation of hair and other keratinous materialcomprising passing carbon 'dioxide into an aqueous solution containing amercaptocarboxylic acid selected from the group consisting ofthioglycollic acid and thiolactic acid and at least one organic baseselected from the group consisting of guanidine, monoethylamine,monoethanolamine, diethanolamine, monoisopropanolamine and morpholineuntil the solution attains a pI-l value from7.5 to 8.5.

,8. A method of imparting a permanent deformation to hair and otherkeratinous material which comprises constraining the material to adesired configuration, treating the constrained material at roomtemperature with an aqueous solution comprising a salt of amercaptocarboxylic acid With at least one organic base selected from thegroup consisting of guanidine, :monoethylamine,

monoethanolamine, diethanolamine, monoisopropanola mine and morpholine,and a carbonate of said organic of a mercaptocarboxyiic acid selectedfrom the group consisting of thioglycollic acid and thiolactic acid Witha mixture of guanidine and gnanidine carbonate, the pH value of thesolution being from 7 to 9.

10. An aqueous solution for use in eifecting the per:

manent deformation of live human hair comprisin a salt of a mercaptoccboxylic acid selected from, the group consisting'of thi glycollic acidand thiolaotic acid with a mixture or" monoethylamine and monoethylaminecarbonate, the pH value of the solutionbeing from 7 to 9.

ilvAn aqueous solution for use'in effecting the permanent dforrna-tionof live human hair, comprisin a; salt of a mercap tocarboxylic acidselectedfrorn the group consisting of thioglycollic acid and thiolacticacid with a mixture of monoethanolamine and monoethanolamine carbonate,the pH value of the solution being from 7 to 9.

12. An aqueous solution for use in efiecting the permanent deformationof live human hair, comprising: a salt of a mercaptocarboxylic acidselected from the group consisting of thioglycollic acid and thiolacticacid with a mixture of diethanolamine and diethanolamine carbonate, thepH value of the solution being from 7 to 9.

13. An aqueous solution for use in effecting the permanent deformationof live human hair, comprising: a salt of a mercaptocarboxylic acidselected from the group consisting of thioglycollic acid and thiolacticacid with a mixture of monoisopropanolamine and monoisopropa- 6 nolaminecarbonate, the pH value of the solution being from 7 to 9.

14. An aqueous solution for use in effecting the permanent deformationof live human hair, comprising: a salt of a mercaptocarboxylic acidselected from the group consisting of thioglycollic acid and thiolacticacid with a mixture of morpholine and morpholine carbonate, the pH valueof the solution being from 7 to 9.

Schnell Mar. 17, 1953 De Mytt et al May 24, 1955

1. AN AQUEOUS SOLUTION FOR USE IN EFFECTING THE PERMANENT DEFORMATION OFHAIR AND OTHER KERATINOUS MATERIAL COMPRISING A SALT OF AMERCAPTOCARBOXYLIC ACID SELECTED FROM THE GROUP CONSISTING OFTHIOGLYCOLIC ACID AND THIOLACETIC ACID WITH AT LEAST ONE ORGANIC BASESELECTED FROM THE GROUP CONSISTING OF GUANIDINE, MONOETHYLAMINE,MONOETHANOLAMINE, DIETHANOLAMINE, MONOISOPROPANOLAMINE AND MORPHOLINEAND A CARBONATE OF SAID ORGANIC BASE, THE PH VALUE OF THE SOLUTIN BEINGFROM 7 TO 9.